TWI589701B - Method for suppressing Ti concentration in steel and method for producing bismuth deoxidized steel - Google Patents
Method for suppressing Ti concentration in steel and method for producing bismuth deoxidized steel Download PDFInfo
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- TWI589701B TWI589701B TW104127002A TW104127002A TWI589701B TW I589701 B TWI589701 B TW I589701B TW 104127002 A TW104127002 A TW 104127002A TW 104127002 A TW104127002 A TW 104127002A TW I589701 B TWI589701 B TW I589701B
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- steel
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- tio
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- slag
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- 229910000831 Steel Inorganic materials 0.000 title claims description 83
- 239000010959 steel Substances 0.000 title claims description 83
- 238000000034 method Methods 0.000 title claims description 23
- 229910000532 Deoxidized steel Inorganic materials 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229910052797 bismuth Inorganic materials 0.000 title claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 51
- 239000002893 slag Substances 0.000 claims description 48
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 21
- 238000007670 refining Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 85
- 239000010936 titanium Substances 0.000 description 73
- 229910052742 iron Inorganic materials 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910005438 FeTi Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- -1 CaCO 3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910002593 Fe-Ti Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910006639 Si—Mn Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002357 osmotic agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
- C21D7/04—Modifying the physical properties of iron or steel by deformation by cold working of the surface
- C21D7/06—Modifying the physical properties of iron or steel by deformation by cold working of the surface by shot-peening or the like
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
- C21C5/54—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/006—Making ferrous alloys compositions used for making ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Description
本發明係關於一種例如於製造矽脫氧鋼等鋼之際之鋼中Ti濃度的抑制方法及使用該抑制方法之矽脫氧鋼的製造方法。 The present invention relates to a method for suppressing Ti concentration in steel, for example, in the production of steel such as niobium-deoxidized steel, and a method for producing niobium-deoxidized steel using the same.
自以往，於盛桶精煉中，已知有藉由對於由轉爐、或電爐所出鋼之熔鋼，添加Al(鋁)或Si(矽)，以進行鋼之脫氧的方法。如此之鋼的脫氧處理中，用以盡可能地減少脫氧後之鋼中的夾雜物，以使鋼之成分適當化的技術正開發中(專利文獻1~6等)。 In the past, in the barrel refining, a method of deoxidizing steel by adding Al (aluminum) or Si (矽) to a molten steel which is produced by a converter or an electric furnace is known. In the deoxidation treatment of such a steel, a technique for reducing the inclusions in the steel after deoxidation as much as possible to optimize the composition of the steel is under development (Patent Documents 1 to 6, etc.).
例如，於專利文獻1，以製造Al團簇少的鋼材為目的，揭示一種使熔渣之組成為CaO+Al2O3≧80%、SiO2≦3%、CaO/Al2O3=1.5~4的技術。又，於專利文獻2，以製造鋸條鋼為目的，揭示一種限制鋼中之Al濃度為0.001~0.002%、並且限制於盛桶施工後之耐火物材質及熔渣組成的技術。 For example, in Patent Document 1, for the purpose of producing a steel material having few Al clusters, it is revealed that the composition of the slag is CaO + Al 2 O 3 ≧ 80%, SiO 2 ≦ 3%, and CaO / Al 2 O 3 = 1.5. ~4 technology. Further, in Patent Document 2, for the purpose of manufacturing a saw blade steel, a technique for limiting the Al concentration in the steel to 0.001 to 0.002% and limiting the composition of the refractory material and the slag after the barrel construction is disclosed.
於專利文獻3，以具有對轉動疲勞所致之破損有良好的耐久性、確保優異之轉動疲勞壽命為目的，揭示一種限制鋼中之Al濃度為0.005%以下的技術。於專利文獻4，以提供一種高清淨度Si脫氧鋼為目的，其可謀求氧化物系夾雜物於熱軋及冷軋步驟安定地伸展及微細化，而揭示一種限制鋼中之Al濃度為0.003%以下的技術。 Patent Document 3 discloses a technique for limiting the Al concentration in steel to 0.005% or less for the purpose of having excellent durability against breakage due to rotational fatigue and ensuring excellent rotational fatigue life. In Patent Document 4, in order to provide a high-definition-purity Si-deoxidized steel, it is possible to stably expand and refine an oxide-based inclusion in a hot rolling and cold rolling step, and to disclose a limit aluminum concentration of 0.003 in a steel. % below the technology.
於專利文獻5，以製造可減低Si脫氧鋼中之總氧濃度為15ppm以下之Si脫氧鋼為目的，揭示一種限制鋼中之Al濃度為0.003%以下、Ti濃度為0.0010%以下、Zr濃度為0.0001%以下、REM濃度為0.0005%以下的技術。再者，於專利文獻6，以提供一種疲勞強度優異之Si脫氧鋼為目的，揭示一種限制鋼中之Al濃度為0.003%以下、Ti濃度為0.003%以下、Zr濃度為0.0010%以下的技術。 In the patent document 5, for the purpose of producing a Si-deoxidized steel having a total oxygen concentration of 15 ppm or less in the Si-deoxidized steel, it is disclosed that the Al concentration in the steel is 0.003% or less, the Ti concentration is 0.0010% or less, and the Zr concentration is 0.0001% or less and a REM concentration of 0.0005% or less. Further, in Patent Document 6, in order to provide a Si-deoxidized steel having excellent fatigue strength, a technique of limiting the Al concentration in the steel to 0.003% or less, the Ti concentration to 0.003% or less, and the Zr concentration to 0.0010% or less is disclosed.
專利文獻1：日本特開2014-037598號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2014-037598
專利文獻2：日本特開2013-224480號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2013-224480
專利文獻3：日本特開2010-7092號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-7092
專利文獻4：日本特開2010-202905號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2010-202905
專利文獻5：日本特開2002-194497號公報 Patent Document 5: Japanese Laid-Open Patent Publication No. 2002-194497
專利文獻6：日本特開2002-167647號公報 Patent Document 6: Japanese Laid-Open Patent Publication No. 2002-167647
若詳查上述之專利文獻1~6，則於部分文獻雖有揭示關於鋼中之Ti濃度的技術，但卻無關於調整熔渣中 TiO2濃度的具體記述。因此，即使使用該等技術，實際上並無法適當地抑制鋼中所含之微量的Ti濃度。亦即，難以抑制鋼中所含之微量之Ti濃度的偏差。 When the above-mentioned Patent Documents 1 to 6 are examined in detail, although some techniques for revealing the Ti concentration in steel are disclosed in some documents, there is no specific description about adjusting the concentration of TiO 2 in the slag. Therefore, even if these techniques are used, it is practically impossible to appropriately suppress the trace amount of Ti contained in the steel. That is, it is difficult to suppress the deviation of the trace amount of Ti contained in the steel.
因此，本發明有鑑於上述問題點，其目的在於提供一種鋼中Ti濃度的抑制方法，其關於鋼中所含之Ti濃度，可抑制其之偏差。 Accordingly, the present invention has been made in view of the above problems, and an object thereof is to provide a method for suppressing Ti concentration in steel, which can suppress variation in Ti concentration in steel.
本發明之鋼中Ti濃度的抑制方法，係於對熔鋼進行盛桶精煉以製造含有Si：0.1~3質量%、Al：0.0001~0.005質量%之矽脫氧鋼時之鋼中Ti濃度的抑制方法，其包含於前述盛桶精煉中對盛桶中之熔渣添加含TiO2之氧化物的步驟，前述盛桶精煉之結束時間點之前述熔渣滿足下述之式(1)~式(7)。 The method for suppressing the Ti concentration in the steel of the present invention is for suppressing the Ti concentration in the steel when the molten steel is refined in a barrel to produce a bismuth deoxidized steel containing Si: 0.1 to 3% by mass and Al: 0.0001 to 0.005% by mass. The method comprises the steps of adding an oxide containing TiO 2 to the slag in the barrel in the foregoing barrel refining, wherein the slag at the end of the barrel refining meets the following formula (1) to 7).
0.5≦CaO/SiO2≦1.8 (1) 0.5≦CaO/SiO 2 ≦1.8 (1)
4質量%≦Al2O3≦20質量% (2) 4% by mass ≦Al 2 O 3 ≦20% by mass (2)
MgO≦15質量% (3) MgO≦15% by mass (3)
1.5質量%≦TiO2≦10質量% (4) 1.5% by mass ≦TiO 2 ≦10% by mass (4)
CaO+SiO2+Al2O3+MgO+TiO2≧90質量% (5) CaO+SiO 2 +Al 2 O 3 +MgO+TiO 2 ≧90% by mass (5)
0.4≦TiO2/MnO≦5 (6) 0.4≦TiO 2 /MnO≦5 (6)
1≦TiO2/T.Fe≦10 (7) 1≦TiO 2 /T.Fe≦10 (7)
(其中，式中以化學式所示之化合物係以該化合物之質量%所表示之含量，T.Fe係以熔渣中之Fe氧化物所含之Fe之質量比所表示之濃度和)。 (wherein the compound represented by the chemical formula in the formula is a content represented by the mass% of the compound, and T.Fe is a concentration expressed by the mass ratio of Fe contained in the Fe oxide in the slag).
又，本發明之矽脫氧鋼之製造方法，係對熔鋼進行盛桶精煉以製造含有Si：0.1~3質量%、Al：0.0001~0.005質量%之矽脫氧鋼的方法，其係藉本發明之鋼中Ti濃度的抑制方法來抑制鋼中Ti之濃度。 Moreover, the method for producing a niobium-deoxidized steel according to the present invention is a method for producing a niobium-deoxidized steel containing Si: 0.1 to 3% by mass and Al: 0.0001 to 0.005 mass% by barrel refining of molten steel. A method for suppressing the Ti concentration in the steel to suppress the concentration of Ti in the steel.
藉由本發明，關於鋼中所含之Ti濃度，可抑制其之偏差。 According to the present invention, the deviation of the Ti concentration contained in the steel can be suppressed.
圖1，係實施例A及比較例D中之熔鐵之[Ti]濃度。 Figure 1 is a [Ti] concentration of molten iron in Example A and Comparative Example D.
圖2，係實施例B及比較例E中之熔鐵之[Ti]濃度。 Figure 2 is a [Ti] concentration of the molten iron in Example B and Comparative Example E.
圖3，係實施例C及比較例F中之熔鐵之[Ti]濃度。 Figure 3 is a [Ti] concentration of the molten iron in Example C and Comparative Example F.
以下，根據圖式說明本發明之實施形態。 Hereinafter, embodiments of the present invention will be described based on the drawings.
於製鋼製程，若以轉爐或電爐結束熔鐵(熔鋼)的精煉，則一般熔鐵被取出至盛桶，而以盛桶進行精煉(盛桶精煉)。於取出至盛桶之熔鋼中，殘存有轉爐或電爐中之脫碳或脫磷所使用之氧。因此，於盛桶精煉等，例如，藉由添加Al至熔鋼，以進行除去熔鋼中之氧的脫氧。以Al脫氧時，由於Al之添加等而於熔鋼中生成之氧化鋁或尖晶石，會作為非金屬夾雜物含於鋼材中。有鑑於此，盡可能地限制Al的添加量，取而代之，有將與氧之親和性較 Al弱的Si添加至熔鋼，藉此進行熔鋼之脫氧的方法。於本發明，係至少以包含藉由將Si添加至熔鋼以進行熔鋼之脫氧處理為對象。 In the steel making process, if the refining of the molten iron (melting steel) is completed by a converter or an electric furnace, the general molten iron is taken out to the barrel and refined in a barrel (refined barrel). The oxygen used for decarburization or dephosphorization in a converter or an electric furnace remains in the molten steel taken out into the barrel. Therefore, in the barrel refining or the like, for example, deoxidation of oxygen in the molten steel is performed by adding Al to the molten steel. When Al is deoxidized, alumina or spinel formed in the molten steel due to the addition of Al or the like is contained in the steel material as a non-metallic inclusion. In view of this, as much as possible to limit the amount of Al added, instead, there will be affinity with oxygen Al weak Si is added to the molten steel, thereby performing a method of deoxidizing the molten steel. In the present invention, at least the deoxidation treatment of the molten steel by adding Si to the molten steel is included.
詳而言之，本發明係以矽脫氧鋼之製造方法為對象，其係對由轉爐、或電爐出鋼之熔鋼進行盛桶精煉，以製造含有Si：0.1~3質量%(表示質量%。以下相同)、Al：0.0001~0.005質量%之矽脫氧鋼。Si濃度之下限值訂為0.1%、Si濃度之上限值訂為3%。若Si濃度超過3%，亦即添加至熔鋼之Si為多，熔鋼會強烈地脫氧，以氧化矽為主成分之非金屬夾雜物會內含於熔鋼中，故其之上限值為3%。又，雖係以轉爐、或電爐進行精煉後進行盛桶精煉為前提，但只要可使盛桶精煉前之熔鋼的碳濃度[C]為2%以下之精煉爐(製鋼爐)，並不限定於轉爐或電爐，不拘精煉爐的種類。 More specifically, the present invention is directed to a method for producing a deuterium-deoxidized steel, which is subjected to barrel refining by a converter or an electric steel tapped steel to produce Si: 0.1 to 3% by mass (indicating mass%) The same as the following), Al: 0.0001 to 0.005 mass% of bismuth deoxidized steel. The lower limit of the Si concentration is set to 0.1%, and the upper limit of the Si concentration is set to 3%. If the Si concentration exceeds 3%, that is, the Si added to the molten steel is much, the molten steel will be strongly deoxidized, and the non-metallic inclusions containing yttrium oxide as the main component will be contained in the molten steel, so the upper limit value It is 3%. In addition, it is premised on refining in a converter or an electric furnace, and the refining furnace (steel furnace) in which the carbon concentration [C] of the molten steel before refining is 2% or less is not It is limited to the converter or electric furnace, regardless of the type of refining furnace.
關於盛桶精煉，該盛桶精煉之結束時間點的熔渣組成，係使CaO/SiO2為0.5以上1.8以下、Al2O3為4%以上20%以下、MgO為15%以下(不含0%)。又，本說明書中，使用「/」、「≦」及「+」之至少一者所表示之式中所記載之例如「CaO」、「SiO2」之化學式，係表示以該化學式所示之化合物之質量比所表示的含量。 Regarding the barrel refining, the composition of the slag at the end of the barrel refining is such that CaO/SiO 2 is 0.5 or more and 1.8 or less, Al 2 O 3 is 4% or more and 20% or less, and MgO is 15% or less (excluding 0%). In the present specification, the chemical formulas such as "CaO" and "SiO 2 " described in the formula indicated by at least one of "/", "≦", and "+" are expressed by the chemical formula. The mass ratio of the compound is expressed as a percentage.
接著，詳細說明熔渣組成。 Next, the slag composition will be described in detail.
若CaO/SiO2未滿0.5，則容易生成以SiO2為主體之非金屬夾雜物，鋼材之疲勞特性惡化，故以0.5為下限。另一方面，若CaO/SiO2超過1.8，則施工於盛桶內側之耐 火物質容易受到熔渣的侵蝕。亦即，耐火物質之侵蝕量增加，起因於耐火物質之侵蝕的非金屬夾雜物會於鋼中增加，故以1.8為上限。 When CaO/SiO 2 is less than 0.5, non-metallic inclusions mainly composed of SiO 2 are easily formed, and the fatigue properties of the steel material are deteriorated. Therefore, 0.5 is the lower limit. On the other hand, if CaO/SiO 2 exceeds 1.8, the refractory substance applied to the inside of the tub is easily corroded by the slag. That is, the amount of erosion of the refractory material increases, and the non-metallic inclusions caused by the erosion of the refractory substance increase in the steel, so the upper limit is 1.8.
若Al2O3低於4%，則Al2O3為相對上較SiO2多的狀態，而容易生成以SiO2為主體的非金屬夾雜物，故以4%為下限。另一方面，若Al2O3高於20%，則容易生成以Al2O3為主體的非金屬夾雜物，使鋼材的疲勞特性惡化，故以20%為上限。 When Al 2 O 3 is less than 4%, Al 2 O 3 is in a state of being more than SiO 2 , and it is easy to form non-metallic inclusions mainly composed of SiO 2 , so 4% is the lower limit. On the other hand, when Al 2 O 3 is more than 20%, non-metallic inclusions mainly composed of Al 2 O 3 are easily formed, and the fatigue properties of the steel material are deteriorated. Therefore, the upper limit is 20%.
MgO，係由施工於盛桶內側之耐火物質不可避免地混入者。或者，MgO係為了使熔渣之熔點或黏性降低所添加者。此處，若MgO超過15%，則會生成以MgO為主體之非金屬夾雜物，使鋼材的疲勞特性惡化，故以15%為上限。 MgO is inevitably mixed by refractory materials applied to the inside of the barrel. Alternatively, MgO is added in order to lower the melting point or viscosity of the slag. Here, when MgO exceeds 15%, non-metallic inclusions mainly composed of MgO are formed, and the fatigue properties of the steel material are deteriorated. Therefore, 15% is an upper limit.
而於本發明，於製造矽脫氧鋼之際，於進行盛桶精煉之際，藉由添加含TiO2之氧化物，使TiO2為1.5~10%。亦即，於熔渣必須含有TiO2，並非作為助熔劑(造縡劑)之雜質而含有，而係有意地添加於熔渣。 In the present invention, in the production of rhodium-removed steel, TiO 2 is made 1.5 to 10% by adding an oxide containing TiO 2 during the barrel refining. That is, the slag must contain TiO 2 and is not contained as an impurity of a flux (osmotic agent), but is intentionally added to the slag.
接著，詳細說明將TiO2添加至熔渣。 Next, the addition of TiO 2 to the slag will be described in detail.
發明人於製造矽脫氧鋼、亦即Si全靜鋼時，為了抑制於盛桶精煉時熔鋼中之Ti濃度，而將含海綿鈦、純鈦、或金屬鈦之FeTi等之合金鐵添加至熔鋼。另外，求出於盛桶精煉時分配至熔渣與熔鐵之比例、亦即Ti分配=(Ti)/[Ti]。又，(Ti)係熔渣中之Ti濃度(質量%)、[Ti]係熔鋼中之Ti濃度(質量%)。 In order to suppress the Ti concentration in the molten steel during barrel refining, the inventors added alloy iron containing titanium sponge, pure titanium, or titanium metal FeTi to the bismuth deoxidized steel, that is, Si total static steel. Fused steel. Further, the ratio of the slag to the molten iron, that is, the Ti distribution = (Ti) / [Ti], is determined in the barrel refining. Further, the Ti concentration (% by mass) in the (Ti)-based molten slag and the Ti concentration (% by mass) in the [Ti]-based molten steel.
其之結果，當將含海綿鈦、純鈦、或鈦之合金鐵直接添加至熔鋼時，Ti分配為200~20000左右之高的值。其顯示即使將含有海綿鈦等純鈦或金屬鈦之FeTi等之合金鐵添加至熔鐵，其之絕大部分會於熔渣中以Ti氧化物存在，表示高價的鈦浪費了。 As a result, when the alloy iron containing titanium sponge, pure titanium, or titanium is directly added to the molten steel, Ti is distributed to a high value of about 200 to 20,000. It shows that even if alloy iron containing FeTi or the like of titanium titanium or titanium metal is added to the molten iron, most of it will exist as Ti oxide in the slag, indicating that expensive titanium is wasted.
又，當於熔渣中含有Fe、Mn、Si等氧化力較Ti弱之元素的氧化物(FeOx、MnO、SiO2等)時，由於所添加之Ti，該等氧化物的一部分會還原。而由於難以預測因該還原所消耗之Ti的量，結果，難以精度佳地控制熔鐵中之Ti濃度、或熔渣組成。 Further, when the slag contains an oxide (FeOx, MnO, SiO 2 or the like) of an element having an oxidizing power such as Fe, Mn or Si which is weaker than Ti, a part of the oxide is reduced by the added Ti. On the other hand, since it is difficult to predict the amount of Ti consumed by the reduction, it is difficult to accurately control the Ti concentration or the slag composition in the molten iron.
因此，發明人發現，由盛桶精煉之初期即於熔渣添加TiO2，由熔渣作為Ti分配至熔鋼者，能以更高精度控制熔鋼中之Ti濃度。又，發現藉由該方法，可抑制高價之金屬Ti或含Ti之合金鐵的使用量。特別是，發現當控制熔鐵中Ti為數ppm至數十ppm之微量濃度時，於該熔渣添加TiO2之方法，較將金屬Ti投入熔鋼的方法，控制精度更高。 Therefore, the inventors have found that the addition of TiO 2 to the slag at the initial stage of the refining of the barrel and the distribution of the slag as Ti to the molten steel can control the Ti concentration in the molten steel with higher precision. Further, it has been found that by this method, the amount of use of expensive Ti or Ti-containing alloy iron can be suppressed. In particular, it has been found that when the amount of Ti in the molten iron is controlled to a small concentration of several ppm to several tens of ppm, the method of adding TiO 2 to the molten slag is more precise than the method of introducing the metallic Ti into the molten steel.
又，為了確實於熔鋼中分配熔存Ti，熔渣之TiO2之濃度必須為1.5%以上、較佳為2%以上。另一方面，若熔渣之TiO2之濃度超過10%，則容易生成以氮化物TiN為主體之非金屬夾雜物，故以10%為限度。 Further, in order to surely distribute the deposited Ti in the molten steel, the concentration of the TiO 2 of the slag must be 1.5% or more, preferably 2% or more. On the other hand, if the concentration of TiO 2 in the slag exceeds 10%, non-metallic inclusions mainly composed of nitride TiN are easily formed, so that the limit is 10%.
再者，於本發明，關於盛桶精煉之結束時間點之熔渣組成，CaO、SiO2、Al2O3、MgO、TiO2之關係，係滿足CaO+SiO2+Al2O3+MgO+TiO2≧90%。熔渣所含之CaO、 SiO2、Al2O3、MgO及TiO2以外之殘部，會不可避免地混入MnO、FeO、Fe3O4、Fe2O3、P2O、V2O5等。為了提升Ti分配的精度，必須使雜質之濃度為未滿10%。亦即，CaO+SiO2+Al2O3+MgO+TiO2≧90%為必須。 Furthermore, in the present invention, regarding the composition of the slag at the end of the barrel refining, the relationship between CaO, SiO 2 , Al 2 O 3 , MgO, and TiO 2 satisfies CaO + SiO 2 + Al 2 O 3 + MgO. +TiO 2 ≧90%. Residues other than CaO, SiO 2 , Al 2 O 3 , MgO and TiO 2 contained in the slag are inevitably mixed with MnO, FeO, Fe 3 O 4 , Fe 2 O 3 , P 2 O, V 2 O 5 Wait. In order to improve the accuracy of Ti distribution, the concentration of impurities must be less than 10%. That is, CaO + SiO 2 + Al 2 O 3 + MgO + TiO 2 ≧ 90% is necessary.
不可避免地混入熔渣之成分中，MgO、以及FeO、Fe3O4及Fe2O3等之Fe之氧化物(T.Fe)，係使Ti分配比之偏差變大的成分。因此，於本發明，規定關於MgO及T.Fe之上下限值。 It is inevitably mixed into the components of the slag, and MgO, and Fe oxide (T.Fe) such as FeO, Fe 3 O 4 and Fe 2 O 3 are components which cause a large variation in the Ti distribution ratio. Therefore, in the present invention, the upper and lower limits of MgO and T.Fe are specified.
於規定該等MnO及T.Fe時，雖考量規定MnO與T.Fe之兩者的合計值，但當為矽脫氧鋼時，必須分開考量MnO與T.Fe。亦即，當為Al全靜鋼時，由於Al還原熔渣的還原力強，故於熔渣中，MnO濃度與Fe氧化物濃度之差少，而當為矽脫氧鋼時，由於還原熔渣之還原力較Al弱，故MnO濃度與Fe氧化物濃度容易產生差。另外，當Mn濃度高時，熔渣中MnO濃度與T.Fe濃度之差會更增大。因此，於本發明之矽脫氧鋼之情形，係分開規定熔渣中之MnO成分與T.Fe成分。 In the case of specifying these MnO and T.Fe, although the total value of both MnO and T.Fe is specified, when 矽deoxidized steel is used, MnO and T.Fe must be considered separately. That is, when Al is completely static steel, since the reducing power of the Al reducing slag is strong, the difference between the MnO concentration and the Fe oxide concentration in the slag is small, and when it is a deuterium deoxidizing steel, the reducing slag is The reducing power is weaker than Al, so the MnO concentration and the Fe oxide concentration are likely to be poor. In addition, when the Mn concentration is high, the difference between the MnO concentration and the T.Fe concentration in the slag is further increased. Therefore, in the case of the deoxidized steel of the present invention, the MnO component and the T.Fe component in the slag are separately specified.
詳而言之，關於MnO，TiO2/MnO必須為0.4以上5以下。關於T.Fe，TiO2/T.Fe必須為1以上10以下。如此，藉由滿足0.4≦TiO2/MnO≦5、1≦TiO2/T.Fe≦10，可抑制Ti分配比的偏差。又，T.Fe係以熔渣中之Fe氧化物所含之Fe之質量比所表示的濃度和。 In detail, regarding MnO, TiO 2 /MnO must be 0.4 or more and 5 or less. Regarding T.Fe, TiO 2 /T.Fe must be 1 or more and 10 or less. Thus, by satisfying 0.4 ≦ TiO 2 /MnO ≦ 5 and 1 ≦ TiO 2 /T.Fe ≦ 10, the variation in the Ti distribution ratio can be suppressed. Further, T.Fe is a concentration obtained by the mass ratio of Fe contained in the Fe oxide in the slag.
以上，藉由本發明，於製造矽脫氧鋼之際，盛桶精煉之結束時間點之熔渣組成，係使CaO/SiO2為0.5 以上1.8以下、Al2O3為4%以上20%以下、MgO為15%以下(不含0%)。又，藉由添加含TiO2的氧化物，使熔渣中之TiO2為1.5~10%。關於熔渣之組成，係滿足CaO+SiO2+Al2O3+MgO+TiO2≧90%、0.4≦TiO2/MnO≦5、1≦TiO2/T.Fe≦10。 As described above, according to the present invention, in the production of the deuterium-deoxidized steel, the composition of the slag at the end of the barrel refining is such that CaO/SiO 2 is 0.5 or more and 1.8 or less, and Al 2 O 3 is 4% or more and 20% or less. MgO is 15% or less (excluding 0%). Further, by adding an oxide containing TiO 2 , the TiO 2 in the slag is 1.5 to 10%. The composition of the slag is such that CaO+SiO 2 +Al 2 O 3 +MgO+TiO 2 ≧90%, 0.4≦TiO 2 /MnO≦5, and 1≦TiO 2 /T.Fe≦10 are satisfied.
藉由滿足上述之熔渣的組成，可使鋼材中之Ti濃度為0.0005%~0.01%。又，關於Ti濃度，原理上亦可使用超過0.01%的Ti濃度，但於該場合，必須使熔渣中所含之TiO2超過10%。於該場合，於熔渣中添加TiO2，較直接將金屬Ti或含Ti之合金投入熔鋼中者更經濟。此外，如上述，當使TiO2超過10%含有時，容易生成以氮化物TiN為主體的非金屬夾雜物。因此，鋼材中之Ti濃度以0.01%為上限。 By satisfying the composition of the slag described above, the Ti concentration in the steel material can be 0.0005% to 0.01%. Further, in principle, a Ti concentration of more than 0.01% may be used for the Ti concentration. However, in this case, it is necessary to make the TiO 2 contained in the slag exceed 10%. In this case, it is more economical to add TiO 2 to the slag than to directly introduce the metal Ti or the alloy containing Ti into the molten steel. Further, as described above, when TiO 2 is contained in an amount exceeding 10%, non-metallic inclusions mainly composed of nitride TiN are easily formed. Therefore, the Ti concentration in the steel is limited to 0.01%.
另一方面，由Mn、Cr、Si等之Ti以外之合金鐵、盛桶之耐火物質、TiO2以外之熔渣原料中之雜質混入Ti時，即使不有意地添加Ti或TiO2，鋼中之Ti濃度會為0.0002~0.0004%左右。本發明係以有意地使熔渣含有TiO2為骨架，故鋼材中之Ti濃度以0.0005%為下限。 On the other hand, when alloy iron other than Ti such as Mn, Cr, or Si, a refractory material of a barrel, or an impurity in a slag raw material other than TiO 2 is mixed with Ti, even if Ti or TiO 2 is not intentionally added, steel The Ti concentration will be about 0.0002 to 0.0004%. The present invention intentionally makes the slag contain TiO 2 as a skeleton, so the Ti concentration in the steel material is 0.0005% as a lower limit.
表1及表2，係彙整以本發明之鋼中Ti濃度之抑制方法進行處理的實施例、與以不同於本發明之方法進行處理的比較例者。 Tables 1 and 2 are examples in which the treatment of the Ti concentration in the steel of the present invention is carried out, and a comparative example which is treated in a manner different from the method of the present invention.
又，表1及表2之「熔渣組成」之各成分之欄所示之 「%」係質量%之意。 In addition, as shown in the column of each component of "slag composition" in Tables 1 and 2 "%" means the quality %.
說明實施例及比較例中之實施條件。 The implementation conditions in the examples and comparative examples will be described.
於實施例及比較例，係使用感應熔解爐將2kg之電解鐵於氧化鋁製之坩鍋內熔解。電解鐵係使用市售品。又，純度不拘。坩鍋材質，雖係使用氧化鐵(Al2O3)，但只要於 1550℃以上之溫度下，可承受熔鋼(熔鐵)或熔渣的侵蝕即可，材質不拘，例如亦可為氧化鎂(MgO)。又，電解鐵之熔解，為了防止熔鐵的氧化，係於Ar氣流中進行。 In the examples and comparative examples, 2 kg of electrolytic iron was melted in a crucible made of alumina using an induction melting furnace. Commercially available products are used for electrolytic iron. Also, the purity is not limited. Although the material of the crucible is made of iron oxide (Al 2 O 3 ), it can withstand the erosion of molten steel (melt iron) or slag at a temperature of 1550 ° C or higher, and the material is not limited, for example, it can be oxidized. Magnesium (MgO). Further, the melting of the electrolytic iron is carried out in the Ar gas flow in order to prevent oxidation of the molten iron.
熔鋼溫度，於原料熔解後，藉由調整感應熔解爐之輸出，保持於1550~1570℃之範圍。成分調整，係於熔鐵，添加既定量之碳粒、矽晶圓碎屑、電解錳、Fe-Cr-C合金，將熔鐵中之[C]、[Si]、[Mn]、[Cr]調整為既定濃度。又，於比較例，將含有Ti分70%之Fe-Ti合金添加於熔鐵，亦實施熔鐵中Ti濃度調整。成分調整用之添加物，只要事先了解目的元素之含有濃度即可，種類不拘，例如，亦可組合Fe-Si合金、Fe-Mn合金、Fe-Si-Mn合金等。 The molten steel temperature is maintained in the range of 1550 to 1570 ° C by adjusting the output of the induction melting furnace after the raw material is melted. The composition is adjusted to the molten iron, adding a certain amount of carbon particles, crucible wafer crumb, electrolytic manganese, Fe-Cr-C alloy, and [C], [Si], [Mn], [Cr in the molten iron. ] Adjust to the established concentration. Further, in the comparative example, an Fe-Ti alloy containing 70% of Ti was added to the molten iron, and the Ti concentration in the molten iron was also adjusted. The additive for the component adjustment may be known in advance as long as the concentration of the target element is contained, and the Fe-Si alloy, the Fe-Mn alloy, the Fe-Si-Mn alloy, or the like may be combined.
熔鐵之成分，係C=0.5~1.1%、Si=0.14~2.3%、〔Mn=0.16~0.92%、Cr=0~1.6%、Al=0.0001~0.005%。 The composition of molten iron is C=0.5~1.1%, Si=0.14~2.3%, [Mn=0.16~0.92%, Cr=0~1.6%, Al=0.0001~0.005%.
又，熔鐵之成分調整後，將具有既定組成之助熔劑40g添加於熔鐵上。 Further, after the composition of the molten iron was adjusted, 40 g of a flux having a predetermined composition was added to the molten iron.
助熔劑係以使其成為既定組成的方式，事先混合市售之氧化物試藥或碳酸化物試藥(SiO2、CaCO3、MgO、Al2O3、MnO2、TiO2)，以150℃燒成8小時。 The flux is mixed with a commercially available oxide reagent or a carbonate reagent (SiO 2 , CaCO 3 , MgO, Al 2 O 3 , MnO 2 , TiO 2 ) in such a manner as to have a predetermined composition, at 150 ° C. Burn for 8 hours.
而添加助熔劑後，以既定溫度保持60分鐘後，切斷感應熔解爐之電源，使坩鍋內之熔鐵及熔渣凝固。之後，由熔鐵及熔渣裁切出既定量之樣品，分別進行各成分分析。 After the addition of the flux, after maintaining at a predetermined temperature for 60 minutes, the power source of the induction melting furnace was turned off to solidify the molten iron and the slag in the crucible. Thereafter, a sample of a predetermined amount was cut out from the molten iron and the slag, and each component was analyzed.
於實施例及比較例中，實施例A、B、C，係以TiO2 作為助熔劑添加之例。另一方面，比較例D、E、F係完全無添加TiO2之例。實施例A-實驗7實施例B-實驗7，係併用TiO2添加與Ti合金添加之例。 In the examples and comparative examples, Examples A, B, and C are examples in which TiO 2 was added as a flux. On the other hand, Comparative Examples D, E, and F were completely free of TiO 2 added. Example A - Experiment 7 Example B - Experiment 7 was an example in which TiO 2 was added in combination with Ti alloy.
實施例A與比較例D，係矽強脫氧鋼，熔鐵之[Ti]濃度目標為0.001%之鋼種群。實施例A與比較例D中，添加FeTi或TiO2之Ti純分總量，為0.48~0.49g。 Example A and Comparative Example D are barely deoxidized steels, and the [Ti] concentration of molten iron is targeted to a steel population of 0.001%. In Example A and Comparative Example D, the total amount of Ti pure fraction of FeTi or TiO 2 added was 0.48 to 0.49 g.
又，實施例B與比較例E，係矽弱脫氧鋼，熔鐵之[Ti]濃度目標為0.007%之鋼種群。實施例B與比較例E中，添加FeTi或TiO2之Ti純分總量，為1.96~1.98g。再者，實施例C與比較例F，係矽弱脫氧Cr添加鋼，熔鐵之[Ti]濃度目標為0.004%之鋼種群。 Further, in Example B and Comparative Example E, it was a weak deoxidized steel, and the [Ti] concentration of the molten iron was a steel population of 0.007%. In Example B and Comparative Example E, the total amount of Ti pure fraction of FeTi or TiO 2 added was 1.96 to 1.98 g. Further, in Example C and Comparative Example F, steel was weakly deoxidized and Cr was added, and the [Ti] concentration target of the molten iron was 0.004% of the steel population.
實施例C與比較例F，添加FeTi或TiO2之Ti純分總量，為1.38~1.40g。又，矽強脫氧鋼、矽弱脫氧鋼、矽弱脫氧Cr添加鋼，皆為矽脫氧鋼。又，雖對「Si強脫氧」、「Si弱脫氧」等用語的定義，並非以[Si]濃度區別，但為了相對比較鋼種群，為求便利而使用該等用語。 In Example C and Comparative Example F, the total amount of Ti pure fraction of FeTi or TiO 2 added was 1.38 to 1.40 g. Moreover, barely deoxidized steel, weakly deoxidized steel, and weakly deoxidized Cr added steel are all deuterium deoxidized steel. Further, although the definitions of terms such as "strong deoxidation of Si" and "wet deoxidation of Si" are not distinguished by the concentration of [Si], these terms are used for convenience in comparison with steel populations.
於實施例及比較例，藉由比較上述同一鋼種群之調整後之熔鐵[Ti]濃度之偏差、亦即標準偏差來進行評價。 In the examples and comparative examples, the evaluation was performed by comparing the deviations of the adjusted molten iron [Ti] concentration of the same steel population, that is, the standard deviation.
於實施例(實施例A、實施例B、實施例C)，熔渣組成，係CaO/SiO2=5~1.8、Al2O3=4~20%、MgO≦15%(不含0)，藉由添加含TiO2之氧化物使TiO2=1.5~10%。又，CaO+SiO2+Al2O3+MgO+TiO2≧90%、0.4≦TiO2/MnO≦5、1≦TiO2/T.Fe≦10。 In the examples (Example A, Example B, and Example C), the composition of the slag is CaO/SiO 2 = 5 to 1.8, Al 2 O 3 = 4 to 20%, and MgO ≦ 15% (excluding 0). TiO 2 = 1.5 to 10% by adding an oxide containing TiO 2 . Further, CaO + SiO 2 + Al 2 O 3 + MgO + TiO 2 ≧ 90%, 0.4 ≦ TiO 2 / MnO ≦ 5, 1 ≦ TiO 2 / T. Fe ≦ 10.
另一方面，於比較例(比較例D、比較例E、比較例 F)，皆未添加含TiO2之氧化物。 On the other hand, in the comparative examples (Comparative Example D, Comparative Example E, and Comparative Example F), no oxide containing TiO 2 was added.
圖1~3，係彙整實施例及比較例之圖。 1 to 3 are diagrams of a summary embodiment and a comparative example.
圖1，係實施例A及比較例D中之熔鐵之[Ti]濃度，圖2，係實施例B及比較例E中之熔鐵之[Ti]濃度，圖3，係實施例C及比較例F中之熔鐵之[Ti]濃度。 Figure 1 is a [Ti] concentration of the molten iron in Example A and Comparative Example D, Figure 2 is a [Ti] concentration of the molten iron in Example B and Comparative Example E, Figure 3 is an Example C and The [Ti] concentration of the molten iron in Comparative Example F.
如圖1所示，若比較實施例A與比較例D，熔鐵之[Ti]濃度之平均值雖大致相同，但於比較例D，標準偏差為0.00144，相對於此，於實施例A，標準偏差可縮小至0.00048。如圖2所示，若比較實施例B與比較例E，熔鐵之[Ti]濃度之平均值雖大致相同，但於比較例D，標準偏差為0.00443，相對於此，於實施例B，標準偏差可縮小至0.00179。再者，如圖3所示，若比較實施例C與比較例F，熔鐵之[Ti]濃度之平均值雖大致相同，但於比較例F，標準偏差為0.00382，相對於此，於實施例C，標準偏差可縮小至0.00119。 As shown in Fig. 1, in Comparative Example A and Comparative Example D, the average value of the [Ti] concentration of the molten iron was substantially the same, but in Comparative Example D, the standard deviation was 0.00144. In contrast, in Example A, The standard deviation can be reduced to 0.00048. As shown in Fig. 2, in Comparative Example B and Comparative Example E, the average value of the [Ti] concentration of the molten iron was substantially the same, but in Comparative Example D, the standard deviation was 0.00443. In contrast, in Example B, The standard deviation can be reduced to 0.00179. Further, as shown in FIG. 3, when Comparative Example C and Comparative Example F were compared, the average value of the [Ti] concentration of the molten iron was substantially the same, but in Comparative Example F, the standard deviation was 0.00382. In Example C, the standard deviation can be reduced to 0.00119.
亦即，藉由進行本發明之鋼中Ti濃度之抑制方法，於Ti濃度控制為0.0005%~0.01%範圍內的鋼中，於實施例，相對於比較例例，可將Ti濃度之偏差，抑制為1/3~2/5左右。 That is, by performing the method for suppressing the Ti concentration in the steel of the present invention, in the steel in which the Ti concentration is controlled to be in the range of 0.0005% to 0.01%, in the examples, the deviation of the Ti concentration can be made with respect to the comparative example. The suppression is about 1/3~2/5.
又，於此次所揭示之實施形態中，未明白揭示之事項例如操作條件、各種參數、構成物之尺寸、重量、體積等，只要不脫離所屬技術領域者一般所實施的範圍，只要為一般的所屬技術領域者，可採用其容易所設想的事項。 Further, in the embodiment disclosed herein, the disclosed matters such as the operating conditions, various parameters, the size, weight, volume, and the like of the constituents are not disclosed as long as they are not in the range generally practiced by those skilled in the art. Those skilled in the art can adopt matters that are easily conceived.
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| CN112280925B (en) * | 2020-10-12 | 2022-02-15 | 马鞍山钢铁股份有限公司 | Titanium element control method for silicon steel steelmaking smelting |
| CN113462847B (en) * | 2021-05-27 | 2022-06-21 | 马鞍山钢铁股份有限公司 | Control method for ultralow titanium content of ultralow-carbon high-aluminum steel |
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| CN102296157B (en) * | 2010-06-23 | 2013-03-13 | 宝山钢铁股份有限公司 | Very low Ti control method of ultralow-carbon aluminum-silicon killed steel |
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